Epitaxial strontium titanate (STO) films have been grown by atomic layer deposition (ALD) on Si(001) substrates with a thin STO buffer layer grown by molecular beam epitaxy (MBE). Four unit cells of STO grown by MBE serve as the surface template for ALD growth. The STO films grown by ALD are crystalline as-deposited with minimal, if any, amorphous SiOx layer at the STO-Si interface. The growth of STO was achieved using bis(triisopropylcyclopentadienyl)-strontium, titanium tetraisopropoxide, and water as the coreactants at a substrate temperature of 250 °C. In situ x-ray photoelectron spectroscopy (XPS) analysis revealed that the ALD process did not induce additional Si–O bonding at the STO-Si interface. Postdeposition XPS analysis also revealed sporadic carbon incorporation in the as-deposited films. However, annealing at a temperature of 250 °C for 30 min in moderate to high vacuum (10-6–10-9 Torr) removed the carbon species. Higher annealing temperatures (>275 °C) gave rise to a small increase in Si–O bonding, as indicated by XPS, but no reduced Ti species were observed. X-ray diffraction revealed that the as-deposited STO films were c-axis oriented and fully crystalline. A rocking curve around the STO(002) reflection gave a full width at half maximum of 0.30° ± 0.06° for film thicknesses ranging from 5 to 25 nm. Cross-sectional transmission electron microscopy revealed that the STO films were continuous with conformal growth to the substrate and smooth interfaces between the ALD- and MBE-grown STO. Overall, the results indicate that thick, crystalline STO can be grown on Si(001) substrates by ALD with minimal formation of an amorphous SiOx layer using a four-unit-cell STO buffer layer grown by MBE to serve as the surface template.